在Tl4-H+ (n = 0∼4) 中:以平面方式四坐标?
Li-Juan Cui1, Xin-Bo Liu1, Hui-Yu Zhang1
1Institute of Atomic and Molecular Physics, Jilin University, Changchun 130023, China.
Inorganic chemistry
|July 12, 2024
概括
在In4H+中研究了平面四坐标 (ptH). 计算表明略有非平面结构是受欢迎的,但由于易于相互转换,挑战传统的化学结合规则,该物种可以被认为是平面的.
科学领域:
- 计算化学计算化学
- 无机化学 无机化学 有机化学
- 量子化学 是一个量子化学.
背景情况:
- 平面超协调分子的概念是一个快速发展的领域.
- 最近的报道表明,In4H+中可能存在平面四坐标 (ptH).
研究的目的:
- 研究 ptH 在 In4H+ 和相关 In-Tl 系统中的结构和能量特性.
- 为了确定这些新型化学物种的稳定性和平面性.
主要方法:
- 高级合集群计算,特别是CCSD.
- 使用 aug-cc-pV5Z/aug-cc-pV5Z-PP 基数组进行精确的能量和频率计算.
- 探索了各种In-Tl组成,其中有一个中心原子.
主要成果:
- 拟议的D4对称的ptH In4H+是一个第一阶段的位点,而不是一个稳定的最小值.
- 一个C4对称的同位素,其中的略高于In4平面,比In4平面稳定0.5kcal/mol.
- 振动平均使得结构可以被认为是有效的平面.
- 在In_nTl_{4-n}H+ (n=0-3) 中,除In2Tl2H+外,pTH结构预计是全球最小值.
- 一个单一的sigma-delocalized相互作用是这些物种平面性和稳定的关键.
结论:
- ptH In4H+系统表现出振动平均平面结构,尽管对非平面同位素有轻微的能量偏好.
- 平面四坐标在混合-系统中是可实现和稳定的,扩大了超坐标化学的范围.
- 这些发现挑战了传统的结合范式,并突出了移位结合在稳定不寻常几何形状方面的重要性.
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